Low zirconium, hafnium-containing compositions, processes for the preparation thereof and methods of use thereof

• US 20060062910A1
• Filed: 10/07/2005
• Published: 03/23/2006
• Est. Priority Date: 03/01/2004
• Status: Abandoned Application

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Meiere, Scott Houston
• Application Number:
  US11/245,104
• Publication Number:
  US 20060062910A1
• Time in Patent Office: Days
• US Class Current: 427/226
• CPC Class Codes: C01G 27/04 Halides
• CPC Class Codes: C01P 2006/80 Compositional purity
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/4402 Reduction of impurities in the source gas
• CPC Class Codes: C23C 18/06 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 18/08 characterised by the deposition of metallic material
• CPC Class Codes: C23C 18/12 characterised by the deposition of inorganic material other than metallic material
• CPC Class Codes: C23C 18/1208 Oxides, e.g. ceramics
• CPC Class Codes: C23C 18/1216 Metal oxides C23C18/1212 takes precedence
• CPC Class Codes: C23C 18/125 Process of deposition of the inorganic material
• CPC Class Codes: C23C 18/1291 by heating of the substrate
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2

Abstract

This invention relates to hafnium-containing compositions having a zirconium concentration of less than about 500 parts per million, a process for producing the hafnium-containing compositions, organometallic precursor compositions containing a hafnium-containing compound and having a zirconium concentration of less than about 500 parts per million, a process for producing the organometallic precursor compositions, and a method for producing a film or coating from the organometallic precursor compositions. The organometallic precursor compositions are useful in semiconductor applications as chemical vapor deposition (CVD) or atomic layer deposition (ALD) precursors for film depositions.

Claims

1. A composition comprising a hafnium-containing compound represented by the formula Hf(R)_m wherein R is the same or different and represents a halogen atom, a pseudohalogen group, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amino group having from 1 to about 12 carbon atoms, an imino group having from 1 to about 12 carbon atoms, a silyl group having from 0 to about 12 carbon atoms, an allyl-like group having from 1 to about 12 carbon atoms, a beta-diketonato group having from 1 to about 12 carbon atoms, or an amidinato group having from 1 to about 12 carbon atoms, m is a value of from 1 to 4, and wherein said composition has a zirconium concentration of less than about 500 parts per million.

3. The composition of claim 1 having a zirconium concentration of less than about 250 parts per million.

4. The composition of claim 1 having a zirconium concentration of less than about 100 parts per million.

5. The composition of claim 1 having a zirconium concentration of less than about 10 parts per million.

6. The composition of claim 1 having a zirconium concentration of less than about 5 parts per million.

7. The composition of claim 1 wherein said hafnium-containing compound is selected from tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(diethylamino)hafnium (TDEAH), hafnium amide, hafnium (IV) tert-butoxide, hafnium (IV) acetylacetonate, bis(ethylcyclopentadienyl)dimethylhafnium or t-butylimidobis(dimethylamino)hafnium.

2. An organometallic precursor composition comprising a hafnium-containing compound represented by the formula Hf(R)_m wherein R is the same or different and represents a halogen atom, a pseudohalogen group, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amino group having from 1 to about 12 carbon atoms, an imino group having from 1 to about 12 carbon atoms, a silyl group having from 0 to about 12 carbon atoms, an allyl-like group having from 1 to about 12 carbon atoms, a beta-diketonato group having from 1 to about 12 carbon atoms, or an amidinato group having from 1 to about 12 carbon atoms, m is a value of from 1 to 4, and wherein said composition has a zirconium concentration of less than about 500 parts per million.

8. A process for producing a composition comprising a hafnium-containing compound represented by the formula Hf(R)_m wherein R is the same or different and represents a halogen atom, a pseudohalogen group, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amino group having from 1 to about 12 carbon atoms, an imino group having from 1 to about 12 carbon atoms, a silyl group having from 0 to about 12 carbon atoms, an allyl-like group having from 1 to about 12 carbon atoms, a beta-diketonato group having from 1 to about 12 carbon atoms, or an amidinato group having from 1 to about 12 carbon atoms, m is a value of from 1 to 4, and wherein said composition has a zirconium concentration of less than about 500 parts per million, which process comprises reacting a hydrocarbon or heteroatom-containing compound with a hafnium halide compound represented by the formula Hf(X)₄ wherein X is the same or different and is a halide and wherein said hafnium halide compound has a zirconium concentration of less than about 500 parts per million, under reaction conditions sufficient to produce said composition.

9. The process of claim 8 wherein said hydrocarbon or heteroatom-containing compound is selected from a lithiated amide, alkoxide, diketonate, cyclopentadienide or imide.

10. The process of claim 8 wherein said hafnium halide compound is selected from HfCl₄, HfF₄, HfBr₄, or HfI₄.

11. The process of claim 8 wherein said hafnium-containing compound is selected from tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(diethylamino)hafnium (TDEAH), hafnium amide, hafnium (IV) tert-butoxide, hafnium (IV) acetylacetonate, bis(ethylcyclopentadienyl)dimethylhafnium or t-butylimidobis(dimethylamino)hafnium.

12. A method for producing a hafnium-containing film, coating or powder having a zirconium concentration of less than about 500 parts per million, which method comprises decomposing an organometallic precursor composition comprising a hafnium-containing compound, thereby producing the film, coating or powder, wherein said hafnium-containing compound is represented by the formula Hf(R)_m wherein R is the same or different and represents a halogen atom, a pseudohalogen group, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amino group having from 1 to about 12 carbon atoms, an imino group having from 1 to about 12 carbon atoms, a silyl group having from 0 to about 12 carbon atoms, an allyl-like group having from 1 to about 12 carbon atoms, a beta-diketonato group having from 1 to about 12 carbon atoms, or an amidinato group having from 1 to about 12 carbon atoms, m is a value of from 1 to 4, and wherein said organometallic precursor composition has a zirconium concentration of less than about 500 parts per million.

13. The method of claim 12 wherein the decomposing of said organometallic precursor composition comprising a hafnium-containing compound is thermal, chemical, photochemical or plasma-activated.

14. The method of claim 12 wherein said organometallic precursor composition comprising a hafnium-containing compound is vaporized and the vapor is directed into a deposition reactor housing a substrate.

15. The method of claim 14 wherein said substrate is comprised of a material selected from the group consisting of a metal, a metal silicide, a semiconductor, an insulator and a barrier material.

16. The method of claim 15 wherein said substrate is a patterned wafer.

17. The method of claim 12 wherein said film, coating or powder is produced by a gas phase deposition.

18. The method of claim 12 wherein said organometallic precursor composition comprising a hafnium-containing compound is selected from tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(diethylamino)hafnium (TDEAH), hafnium amide, hafnium (IV) tert-butoxide, hafnium (IV) acetylacetonate, bis(ethylcyclopentadienyl)dimethylhafnium or t-butylimidobis(dimethylamino)hafnium.

19. A mixture comprising (i) a composition comprising a hafnium-containing compound represented by the formula Hf(R)_m wherein R is the same or different and represents a halogen atom, a pseudohalogen group, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amino group having from 1 to about 12 carbon atoms, an imino group having from 1 to about 12 carbon atoms, a silyl group having from 0 to about 12 carbon atoms, an allyl-like group having from 1 to about 12 carbon atoms, a beta-diketonato group having from 1 to about 12 carbon atoms, or an amidinato group having from 1 to about 12 carbon atoms, m is a value of from 1 to 4, and wherein said composition has a zirconium concentration of less than about 500 parts per million, and (ii) one or more different organometallic compounds.

20. The mixture of claim 19 wherein said one or more other organometallic compounds are selected from a ruthenium-containing, tantalum-containing or molybdenum-containing organometallic compound.